Black sulphurized naphthol dyes



Patented Sept. 6, 1927.

PATENT. OFFICE.

CHARLES HENBI-HABSCHQLK, OF PARIS, FRANCE.

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No Drawing. Application filed larch 11, 1924, Serial No. 698,568, and in France Karen 18, 1928.

The invention resides in the fact that when heating at a high temperature with alkaline polysulrghids, the condensation productsobtained y the reaction of anhydrous chlo- 8 rides, such as aluminium, ferric or other chlorides, on mono or polyhydroxyl denvatives containing preferably naphthalene nuclei (betanaphthol, dihydroxynaphthalene 2-7, betadinaphthol, etc.) black dyestuffs 1 are obtained which act as vatting dyestuffs and possess a fair resistance against soap Washing and chlorine. I

The naphthalene monoor poly-hydroxyl derivatives referred to herein have the general formula:

R(OH)..,

naphthalene compound is betanaphthol, and.

of a poly naphthalene compound is betadinaphthol.

The following are examples of putting the invention into practice; obviously the amounts of reacting agents set forth in these examples are not absolute but may vary within fairly wide limits.

Ewample 1.-A- black dyestufi from beta-' naphthol': One part of betanaphthol thoroughly mixed with three parts of pulverized anhydrous aluminium chloride is heated for one hour at 220C. (the temperaturie being takenwithin the mass)..."

' Thismixture is pulverized, then treated with acid water and finally washed. The

mixture. is furthermore washed with dilute soda solution which has almost no solvent action. f

The residue is brown-black. It is insoluble in a-lkalies'. It is then melted with a polysulphide, e. g. in the following manner:

5 arts of the brown-black residue are mixe with a melted mixture of 5 parts of crystallized sodium sulphide, "10 parts of sulphur and three parts of water, heated to 250 C. The temperatureis progressively raised up to 305310 C. and kept so for approximately one hour.

The mass thus obtained is afterward ground, thoroughly washed with water and then dried. A lack compound is obtained containing an excess 'of sulphur which is sublimed oil by heating at 250 C.

The compound dissolves in an alkaline hydrosulphite. The vat liquor is brownblack. Cotton is dyed black.

Example 2.-A black dyestufi from dihydroxynaphthalcne (2 -7). One part of dihydroxynaphthalene '(2-7) thoroughly mixed with 4 parts of anhydrous aluminium chloride, is heated at 220 C. for one hour.

The swollen mass thus obtained is decomposed by means of diluted hydrochloric acid and thoroughly washed with dilute caustic soda solution in order to eliminatev the unattacked dihydroxynaphthalene.

, The remainder, insoluble in soda, is melted with: 1 part of crystallized sodium sulphide, 2 parts of sulphur, A), part ofwater, and the mass is heated for approximately ha'lf an hour at'a temperature of 305310 C.

The obtained mass is afterwards washed with water, dried, and heated by any known means in order .to eliminate the sulphur in excess.

The resultant compound dissolves in an alkaline hydrosulphite producing a brownblack vat liquor tints. 1'

Example 3.A black dyestufi frombeta dinaphthol- It is known that'betadinaphthol is easily obtained with a nearly by adding-ground betanap thol to a'diluted and hot solution of ferric chloride.

When a thorough mixture of'anhydrousv pulverized aluminium chloride and of very dry betadinaphthol is heated, the temperature and the time of reaction bein such that the mass no longer contains dihy lroxyperylene '1--12 or corresponding perylene-- quinone, a compound is obtained which, when heated afterwards with sulphur and sodiumsulphide, produces a black dyestufi I acting as a vatting dyestufi.

This dyestuif differs from that described in French Letters Patent No. 564,704, filed on January 6th, 1923, in that it 'vesa blackish vat liquor not having a vio et tinge and does not dissolve in. hot concentrated sulphuric acid; while the dyestufl' derived from dihydroxyperylene and described in the aforesaid patent gives a violet-tingedv vat liquor, and a blue-violet solution in hot concentrated sulphuric acid.

In order to obtain this black dyestufi from. betadinaphthol, one part of betadinaphthol which dyes cotton in black uantitative yield is thoroughly mixed with three parts of finely pulverized anhydrous aluminium chloride and is heated at a temperature (taken within the mass) of approximately l80220 C. up to the time when a test specimen taken from the mass shows that the dihydroxyperylene (1-12) and the corresponding perylenequinone (1-12) have completely disappeared.

This disappearance is shown by the absence of any solution in hot acetic acid, in

alkaline sodium hydrosulphite and even inof crystallized sodium sulphide, two parts of flour of sulphur and one half part of water. temperature of 250 C. is reached, one part of the previous intermediate compound is admixed thereto.

The mixture thus completed is then heated during approximately half an hour up to SOS-310 C. (the temperature being taken in the metallic heating bath).

The molten mass is ground and heated with hot water, then filtered, washed, and the sulphur in excess is eliminated by any convenient known means, for example by heating at 250 C., in order that the sulphur be sublimed off.

What I claim is:

1. Black vatting dyestuif, obtained by the action of an alkaline polysulphide on a condensation compound obtained by the reaction of an anhydrous chloride which is a re- The mixture is melted and when a ducing agent upon an hydroxy-naphthalene derivative.

2. Black dyestufi acting as a vatting dyestuff, obtained by the action of an alkaline polysulphide on a condensation compound obtained b the reaction of an anhydrous chloride w ich is a reducing agent upon betadinaphthol.

3. Black dyestufi' acting as a vatting dyestufi', obtained by the action of an alkaline polysulphide on a condensationcompound obtained by the reaction of anhydrous aluminium chloride upon an hydroxy-naphthalene derivative.

4. A process for the manufacture of dyestuffs, which consists in effecting a reaction between an anhydrous chloride which is a reducing agent and a hydroxy-naphthalene derivative, and thereafter treating the resultant product with an alkaline polysulphide.

5. A rocess for the manufacture of a dyestufi' W ich consists in effecting a reaction between an anhydrous chloride which is a reducing agent and a hydroxy-derivative of a betahydroxynaphthalene, and thereafter treating the resultant product with an alkaline polysulphide. V

6. A process for the manufacture of a dyestuff which consists in effecting a reaction between aluminum chloride and a naphthalene derivative and thereafter treating the resultant product with an alkaline polysulphide..

7. A process for the manufacture of a dyestuif which consists in heating betadinaphthol with anhydrous aluminum chloride up to 180 C.-220 C. and for such a time that dihydroxyperylene (112) and the corresponding perylene quinone disappear, washing the obtained mass, and melting the said mass with sulfur and sodium sulphide.

In testimony whereof I affix my signature.

CHARLES HENRI MARSGHALK. 

